HP 129Xe Research Articles

A novel NMR instrument for the in-situ monitoring of the absolute polarization of laser-polarized 129Xe

A new fully digital and home-built NMR (Nuclear Magnetic Resonance) spectrometer working at very-low magnetic field (4.5 mT) is presented. This spectrometer was initially dedicated for the in situ measurement of the absolute polarization of hyperpolarized 129Xe. It allows detection and acquisition of NMR signals of proton (1H) at 190 kHz and of hyperpolarized xenon-129 (HP 129Xe) at 50 kHz. In this new NMR instrument, we replaced as much analog electronics as possible by digital electronic and software. Except for the power amplifier and the preamplifier, the whole system is digital. The transmitter is based on the use of a Direct Digital Synthesizer (DDS) board. The receiving board allows direct digitalization of the NMR signals thanks to an 8-bits analog-to-digital converter (ADC) clocked at 100 MHz. Decimation is preformed to dramatically improve the ADC resolution so as the final achieved effective resolution could be as high as 14-bits at 5 MHz sampling frequency. NMR signals are then digitally downconverted (DDC). Low-pass decimation filtering is applied on the base-band signals (I/Q) to enhance much more the dynamic range. The system requires little hardware. The transmitter and the receiver are controlled using Labview environment. It is a versatile, flexible and easy-to-replicate system. This was actually one of underlying ideas behind this development. Both 1H and hyperpolarized 129Xe NMR signals were successfully acquired. The system is used for the measurement of the absolute polarization of hyperpolarized 129Xe in hyperpolarizing experiments for the brain perfusion measurements. The high degree of flexibility of this new design allows its use for a large palette of other potential applications.

Distribution and modification of sorption sites in amphiphilic calixarene-based solid lipid nanoparticles from hyperpolarized 129Xe NMR spectroscopy.

The site distribution and accessibility in amphiphilic calixarenes-based solid lipid nanoparticles were determined as a function of lipid chain length using in situ 129Xe NMR spectroscopy with flowing hyperpolarized Xe gas. The study illustrates that host cavities in as-prepared materials are increasingly occluded by the lipid chain for compounds with chain lengths from C6 to C12 and are almost completely occluded for C14 and C16 chain lengths. Host cavities present at the surface of the particles are still accessible to small atoms (xenon) and organic molecules (methylene chloride, etc). The Xe spectra show that the accessible void space can be increased remarkably by exposure of the particle surface to suitably sized guest molecules that appear to displace the occluding hydrocarbon chains from the host cavities by competitive adsorption. This postsynthesis treatment thus modifies the state of self-assembly and improves sorption capability. The HP Xe NMR approach presented is suitable for small samples (a few milligrams) of SLNs, likely also for other biomaterials such as vesicles, model membranes, etc.

Investigating hyperpolarized 129Xe and CPMAS for spin polarization transfer to surface nuclei: a model study

Several experimental techniques have been developed to utilize spin-polarized xenon gas for sensitivity and selectivity enhancement in surface studies using solid-state NMR. Although previously reported as a viable spin polarization transfer mechanism, the details of high-field cross-polarization (CP) have not been thoroughly investigated. We recently reported observations of CP from an adsorbed layer of hyperpolarized xenon (HP Xe) to a variety of surface nuclei at temperatures as high as 323 K [J. Am. Chem. Soc. 105 (2001) 1412]. In this paper, we investigate many of the issues associated with HP Xe surface CP studies, including polarization transfer kinetics and the effects of temperature on the dynamics. Protonated and methylated silica samples are used as model systems for comparison. A comparison of the rate analysis data from CP and SPINOE (Spin Polarization-Induced Nuclear Overhauser Effect) experiments provides information on the origin of the difference in polarization transfer efficiencies between the two techniques. Lineshape analysis of 1H spectra for CP and SPINOE experiments demonstrates the difference in selectivity of methods due to longer SPINOE evolution times that lead to greater spin diffusion. The results of this work help to assess the viability of HP Xe CP as a surface analysis technique.